HCID 88777142, 화합물 → HCID 70617022, 화합물

HRID 1657423노트

반응식

HRID 1657423 반응식
C([C:3]1[CH:8]([C:9]([O:11][CH:12]([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)[C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)=[O:10])[N:7]2[C:25](=[O:36])[CH:26]([NH:27][C:28](=[O:35])[CH2:29][C:30]3[S:31][CH:32]=[CH:33][CH:34]=3)[C@H:6]2[S:5][CH:4]=1)=O>C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cl-].[Rh].C1(C)C=CC=CC=1>[CH:12]([O:11][C:9]([C:8]1[N:7]2[C:25](=[O:36])[CH:26]([NH:27][C:28](=[O:35])[CH2:29][C:30]3[S:31][CH:32]=[CH:33][CH:34]=3)[C@H:6]2[S:5][CH2:4][CH:3]=1)=[O:10])([C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1)[C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1

참가 물질

4

반응물 1

HCID 88777142HCID 88777142, 화합물

생성물 1

HCID 70617022HCID 70617022, 화합물

시약·촉매·용매 2

HCID 84599Chlorotris(triphenylphosphine)rhodium(I)촉매HCID 1140Toluene용매

실험 절차

A mixture of the benzhydryl ester from Example 28 (2.5 g, 4.79 mmol), tris-(triphenylphosphine)chlororhodium (3.5 g. 4.79 mmol) and dry toluene (75 ml) was refluxed under nitrogen for 5.5 hours. The reaction mixture was cooled. The rhodium complex was removed by filtration and the filtrate was poured slowly into petroleum ether (250 ml) with stirring. The precipitated solid, which was a mixture of rhodium complex and product, was collected. The product was purified by chromatography on a silica gel column (250 g) using 99:0.5 chloroform:ethyl acetate as eluent. Fractions of 4.5 ml were collected; fractions 1-47 discarded, 48-66 contained bis-(triphenylphosphine)carbonylchlororhodium, and 67-198 contained the product. NMR data indicated the product after chromatography to be the Δ3 isomer instead of the Δ2 isomer. A decoupling experiment showed the 2-methylene group at 3.3 ppm. to be coupled with the 3-proton at 6.6 ppm.

후처리

  1. temperaturewas refluxed under nitrogen for 5.5 hours
  2. temperatureThe reaction mixture was cooled
  3. customThe rhodium complex was removed by filtration
  4. additionthe filtrate was poured slowly into petroleum ether (250 ml)
  5. additiona mixture of rhodium complex and product
  6. customwas collected
  7. customThe product was purified by chromatography on a silica gel column (250 g)
  8. customFractions of 4.5 ml were collected

출처 및 근거

ORD 기록
ord-ebc9d2f869d24e70b504b4fd08b1418f
출처 데이터셋
uspto-grants-1976_06
특허 번호
US03960852

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